Bicyclic conjugated diene polymer and bicyclic conjugated diene copolymer

ABSTRACT

A bicyclic conjugated diene polymer obtained by polymerizing a monomer (M) comprising at least one kind of bicyclic conjugated diene monomer represented by formula (I), and a bicyclic conjugated diene copolymer obtained by copolymerizing monomer (M) with at least one kind of unsaturated compound other than said monomer:                  
 
wherein, R 1  to R 6  are the same or different and are each hydrogen, halogen, or alkyl or halogenated alkyl of 1 to 20 carbon; n and m are each an integer of from 0 to 10; X 1 , X 2 , Y 1  and Y 2  are the same or different from each other and are each hydrogen, halogen or alkyl or halogenated alkyl of 1 to 20 carbon; and, when m or n is 2 or more, each of mX 1 &#39;s, mX 2 &#39;s, nY 1 &#39;s and nY 2 &#39;s are the same or different.

TECHNICAL FIELD

The present invention relates to a cyclic conjugated diene polymer and acyclic conjugated diene copolymer, particularly to a bicyclic conjugateddiene polymer and a bicyclic conjugated diene copolymer.

BACKGROUND ART

In recent years, polymers having a main chain of cyclic hydrocarbonskeleton are drawing attention as a polymer material which is superiorin heat resistance and mechanical strengths owing to the rigid structureand further superior in optical properties, electrical properties, etc.Such polymers are classified into two groups from the main chainstructures which affect the properties. The first group is norbornenetype compound metathesis polymers (see, for example, the third chapterof “Synthesis of Polymers” by R. H. Grubbs, published from Wiley VCH in1999). These polymers have a structural feature of having spacermoieties of chain skeleton between units of bulky cyclic skeleton. Thesecond group is polymers constituted by a cyclic skeleton alone andhaving no spacer moiety. They are, for example, a norbornene typecompound vinylene-type polymer (see, for example, JP-A-3205408,JP-4-63807 and JP-A-5-262821); a cyclopentene polymer (see, for example,JP-A-3-139506, WO 99/50320, and “Macromolecules” 1998, 31, 6705); acyclopentadiene polymer (see, for example, “Macromolecules” 2001, 34,3176); and a 1,3-cyclohexadiene polymer (see, for example,JP-A-7-247321, JP-A2000-26581 and JP-A-2000-351885). However, polymerswhich are sufficient in practical performances of solubility insolvents, heat resistance, mechanical strengths and the like have notbeen developed yet.

Of these polymers, the 1,3-cyclohexadine polymer has a high glasstransition temperature of 170° C. and a high solubility in solvents andis hopeful as a next-generation resin. However, the polymer has a rigidcis structure and is bulky three-dimensionally, and accordingly thepolymerization process for production thereof is limited. Recently,there have been developed polymerization processes such as anionicpolymerization using a butyl lithium/tetramethylethylenediamine catalyst(see, for example, JP-A-7247321), nickel catalyst coordinationpolymerization (see, for example, JP-A2000-26581, JP-A-2000-351885, and“Chemical Communications” 2000, 22072208), and the like; however, thecatalysts used therein are still limited. Further, 1,3-cyclohexadieneper se is difficult to produce industrially. For example,dehydrogenation of cyclohexene (see, for example, JP-A-7-196737) isinferior in conversion and selectivity and has a difficulty inseparation of byproducts; further, it has a detrimental drawback in thatthere is by-produced 1,4-cyclohexadiene which impairs polymerization of1,3-cyclohexadiene. There is also a process for producing1,3-cyclohexadiene via cyclohexene chloride (see, for example,JP-A-11-189614); however, this process employs several steps andmoreover gives a low yield and, therefore, is far from satisfactionindustrially.

Hence, the first object of the present invention is to provide a cyclicdiene polymer which is produced from a cyclic conjugated diene monomereasy to produce and high in polymerization activity, additionally hashigh heat resistance and high mechanical strengths and shows goodsolubility in solvents.

Olefins having a cyclic hydrocarbon skeleton are used as a raw materialfor the above-mentioned polymers of high performances. By using, inparticular, a cyclic diolefin, the polymer obtained can be imparted withfurther functions. For example, a cyclic non-conjugated diolefin such asdicyclopentadiene, vinylnorbornene, ethylidenenorbornene or the like hastwo kinds of unsaturated bonds of different reactivity; therefore,polymerization is possible with one unsaturated bond and functions canbe imparted with the other unsaturated bond. In the case of, forexample, ethylidenenorbornene which is widely used industrially as thethird component of ethylene/propylene/diene rubber (EPDM) [see, forexample, pp. 120 to 122 of “Basis of Rubber Technology (New Edition)”published from The Society of Rubber Industry, Japan on 2002, and pp.130 to 139 of “Handbook of Rubber Industry (New Edition)” published fromThe Society of Rubber Industry, Japan on 1994], it is considered thatthe unsaturated bond of norbornene ring reacts during copolymerizationand the unsaturated bond of ethylidene group reacts during vulcanizationof rubber. When a difference in reactivity between two kinds ofunsaturated bonds is utilized, however, with the result that thedifference is not sufficiently large, the two unsaturated bonds mayreact during polymerization to form a three-dimensional crosslink, whichmay cause gelling.

Meanwhile, a conjugated diene compound is characterized in that thepolymer obtained therefrom contains remaining unsaturated bonds always.The remaining unsaturated bonds are utilized for secondary reaction suchas crosslinking, vulcanization or the like, or for imparting functionsby chemical conversion such as hydrogenation, epoxidization,halogenation, arylation, hydration, carbonylation or the like.

Of various conjugated diene compounds, compounds having a cyclichydrocarbon skeleton, i.e. cyclic conjugated dienes are expected as avery useful compound; however, examples of such cyclic conjugated dienesare very few and only 1,3-cyclohexadiene or so is mentioned (seeMacromolecular Chemistry and Physics, U.S., 2001, 202, pp. 409 to 412,and Journal of Polymer Science: Part B: Polymer Physics, U.S., 1998,Vol. 36, pp. 1657 to 1668). Moreover, as mentioned above, the1,3-cyclohexadiene per se is difficult to produce industrially.

Thus, there is strongly desired, for its industrial usefulness, acopolymer which is obtained by copolymerization of a cyclic conjugateddiene of high polymerizability and easy production with otherunsaturated compound.

Hence, the second object of the present invention is to provide a cyclicdiene copolymer obtained by copolymerization of a cyclic conjugateddiene monomer of easy production and high polymerization activity, withan unsaturated compound.

DISCLOSURE OF THE INVENTION

The present inventors had made strenuous efforts in order to solve theabove problems. As a result, the present inventors found that a bicyclicconjugated diene monomer easily obtained by isomerization of a bicyclicnon-conjugated diene has high reactivity and gives a bicyclic conjugateddiene polymer having a structure which had not heretofore been reported,additionally a high glass transition temperature and further thatcopolymerization of the above bicyclic conjugated diene monomer withother unsaturated compound provides a bicyclic conjugated dienecopolymer having a structure which had not heretofore been reported.This finding has led to the completion of the present invention.

The first aspect of the present invention lies in the followings:

[1] A bicyclic conjugated diene polymer obtained by polymerizing amonomer comprising at least one kind of bicyclic conjugated dienemonomer represented by the following general formula (I):

wherein in the above general formula (I), R₁, R₂, R₃, R₄, R₅ and R₆ maybe the same or different from each other and are each a hydrogen atom, ahalogen atom, or an alkyl or halogenated alkyl group of 1 to 20 carbonatoms; n and m are each an integer of from 0 to 10; X₁, X₂, Y₁ and Y₂may be the same or different from each other and are each a hydrogenatom, a halogen atom, or an alkyl or halogenated alkyl group of 1 to 20carbon atoms; and, when m or n is 2 or more, each of mX₁'s, mX₂'s, nY₁'sand nY₂'s may be the same or different from each other.

[2] A bicyclic conjugated diene polymer according to the above [1],wherein the bicyclic conjugated diene monomer comprisesbicyclo[4.3.0]-2,9-nonadiene, i.e. a compound of the general formula (I)in which R₁=R₂=R₃=R₄=R₅=R₆=H, n=2, m=1, and X₁=X₂=Y₁=Y₂=H.

[3] A bicyclic conjugated diene polymer according to the above [1],wherein the bicyclic conjugated diene monomer comprisesbicyclo[4.3.0]-2,9-nonadiene, i.e. a compound of the general formula (I)in which R₁=R₂=R₃=R₄=R₅=R₆=H, n=2, m=1, and X₁=X₂=Y₁=Y₂=H andbicyclo[4.3.0]-1,8-nonadiene, i.e. a compound of the general formula (I)in which R₁=R₂=R₃=R₄=R₅=R₆=H, n=1, m=2, and X₁=X₂=Y₁=Y₂=H.

[4] A bicyclic conjugated diene polymer according to the above [2] or[3], wherein the bicyclic conjugated diene monomer is a part or thewhole of the isomerization products of bicyclo-[4.3.0]-3,7-nonadiene.

[5] A bicyclic conjugated diene polymer according to the above [1],wherein the bicyclic conjugated diene monomer comprisesbicyclo[4.3.0]-3-methyl-2,9-nonadiene, i.e. a compound of the generalformula (I) in which R₁=R₂=R₃=R₄=R₆=H, R₅=CH₃, n=1, m=2, andX₁=X₂=Y₁=Y₂=H.

[6] A bicyclic conjugated diene polymer according to the above [1],wherein the bicyclic conjugated diene monomer comprisesbicyclo[4.3.0]-3-methyl-2,9-nonadiene andbicyclo[4.3.0]-3-methyl-1,3-nonadiene, which are compounds of thegeneral formula (I) in which R₁=R₂=R₃=R₄=R₆=H, R₅=CH₃, n=1, m=2, andX₁=X₂=Y₁=Y₂=H.

[7] A bicyclic conjugated diene polymer according to the above [5] or[6], wherein the bicyclic conjugated diene monomer is a part or thewhole of the isomerization products ofbicyclo-[4.3.0]-3-methyl-3,7-nonadiene.

[8] A modified bicyclic conjugated diene polymer obtained by chemicalconversion of a bicyclic conjugated diene polymer set forth in any ofthe above [2] to [7].

The second aspect of the present invention lies in the followings.

[1] A bicyclic conjugated diene copolymer obtained by copolymerizing amonomer comprising at least one kind of bicyclic conjugated dienemonomer represented by the following general formula (I), with at leastone kind of unsaturated compound other than said monomer:

wherein in the above general formula (I), R₁, R₂, R₃, R₄, R₅ and R₆ maybe the same or different from each other and are each a hydrogen atom, ahalogen atom, or an alkyl or halogenated alkyl group of 1 to 20 carbonatoms; n and m are each an integer of from 0 to 10; X₁, X₂, Y₁ and Y₂may be the same or different from each other and are each a hydrogenatom, a halogen atom, or an alkyl or halogenated alkyl group of 1 to 20carbon atoms; and, when m or n is 2 or more, each of mX₁'s, mX₂'s, nY₁'sand nY₂'s may be the same or different from each other.

[2] A bicyclic conjugated diene copolymer according to the above [1],wherein the bicyclic conjugated diene monomer comprisesbicyclo[4.3.0]-2,9-nonadiene, i.e. a compound of the general formula (I)in which R₁=R₂=R₃=R₄=R₅=R₆=H, n=2, m=1, and X₁=X₂=Y₁=Y₂=H.

[3] A bicyclic conjugated diene copolymer according to the above [1],wherein the bicyclic conjugated diene monomer comprisesbicyclo[4.3.0]-2,9-nonadiene, i.e. a compound of the general formula (I)in which R₁=R₂=R₃=R₄=R₅=R₆=H, n=2, m=1, and X₁=X₂=Y₁=Y₂=H andbicyclo[4.3.0]-1,8-nonadiene, i.e. a compound of the general formula (I)in which R₁=R₂=R₃=R₄=R₅=R₆=H, n=1, m=2, and X₁=X₂=Y₁=Y₂=H.

[4] A bicyclic conjugated diene copolymer according to the above [2] or[3], wherein the bicyclic conjugated diene monomer is a part or thewhole of the isomerization products of bicyclo-[4.3.0]-3,7-nonadiene.

[5] A bicyclic conjugated diene copolymer according to any of the above[1] to [4], wherein the unsaturated compound is at least one kindselected from olefins and diolefins all of 2 to 10 carbon atoms.

[6] A bicyclic conjugated diene copolymer according to any of the above[1] to [5], wherein the unsaturated compound is at least one kindselected from butadiene, isoprene, piperylene, chloroprene,acrylonitrile, ethylene, propylene, isobutene and styrene.

[7] A modified bicyclic conjugated diene copolymer obtained by chemicalconversion of a bicyclic conjugated diene copolymer set forth in any ofthe above [1] to [6].

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a ¹HNMR (400 MHz) chart of the monomers mixture obtained inProduction Example 1.

FIG. 2 is a ¹³CNMR (100 MHz) chart of the monomers mixture obtained inProduction Example 1.

FIG. 3 is a ¹HNMR (400 MHz) chart of the monomers mixture obtained inProduction Example 2.

FIG. 4 is a ¹³CNMR (100 MHz) chart of the monomers mixture obtained inProduction Example 2.

FIG. 5 is a ¹HNMR (400 MHz) chart of the polymer obtained in Example 2.

FIG. 6 is a ¹³CNMR (100 MHz) chart of the polymer obtained in Example 2.

FIG. 7 is a ¹HNMR (400 MHz) chart of the polymer obtained in Example 5.

FIG. 8 is a ¹³CNMR (100 MHz) chart of the polymer obtained in Example 5.

FIG. 9 is a ¹HNMR (400 MHz) chart of the polymer obtained in Example 7.

FIG. 10 is a ¹³CNMR (100 MHz) chart of the polymer obtained in Example7.

FIG. 11 is a ¹HNMR (400 MHz) chart of the polymer obtained in Example 8.

FIG. 12 is a ¹³CNMR (100 MHz) chart of the polymer obtained in Example8.

FIG. 13 is a ¹HNMR (400 MHz) chart of the polymer obtained in Example 9.

FIG. 14 is an IR chart of the copolymer obtained in Example 9.

FIG. 15 is an IR chart of the copolymer obtained in Example 10.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, explanation is made in detail on the bicyclic conjugateddiene polymer according to the first aspect of the present invention.

The bicyclic conjugated diene polymer of the present invention is apolymer comprising, as the structural unit, a bicyclic conjugated dienemonomer of the general formula (I), and the structure of the polymer isnot restricted. As the bonding form of the polymer of the presentinvention, there can be mentioned, for example, a bond between(n+4)-membered ring and (m+4)-membered ring, a bond between(m+4)-membered ring and (m+4)-membered ring, and a bond between(n+4)-membered ring and (n+4)-membered ring, in the bicyclic conjugateddiene monomer. When the bicyclic conjugated diene monomer comprises, forexample, bicyclo[4.3.0]-3-methyl-2,9-nonadiene andbicyclo[4.3.0]-3-methyl-1,3-nonadiene, which are compounds of thegeneral formula (I) wherein R₁=R₂=R₃=R₄=R₆=H, R₅=CH₃, n=1, m=2, andX₁=X₂=Y₁=Y₂=H, there may also be included a bond between the 5- or6-membered ring of bicyclo[4.3.0]-3-methyl-2,9-nonadiene and the6-membered ring of bicyclo[4.3.0]-3-methyl-1,3-nonadiene. These bondingforms may be present at random or all of them may be present. Inproduction of the bicyclic conjugated diene polymer of the presentinvention, as in production of a butadiene polymer, there are formedeither or both of the 1,4-bond and 1,2-bond of the bicyclic conjugateddiene monomer of the general formula (I). Incidentally, when the1,4-bond is formed, it can have a cis structure and a trans structure.

In production of the bicyclic conjugated diene polymer of the presentinvention, there is usually obtained a polymer having a weight-averagemolecular weight of about 500 to 100,000. Depending upon theapplication, however, there can preferably be used a polymer of about1,000 or more, further about 10,000 or more. There is usually obtained apolymer having a glass transition temperature of up to about 170° C.,and there is usually used a polymer of about 90° C. or more and,depending upon the application, there is preferably used a polymer ofabout 130° C. or more, further about 150° C. or more.

As the bicyclic conjugated diene monomer of the present inventionrepresented by the general formula (I), i.e. the conjugated diene havinga bicyclo[2+n.2+m.0] skeleton, there can be mentioned, for example,bicyclo[4.4.0]-1,9-decadiene, bicyclo[4.3.0]-2,9-nonadiene,bicyclo[4.3.0]-1,8-nonadiene, bicyclo[3.3.0]-1,7-octadiene,bicyclo[4.3.0]-X-methyl-2,9-nonadiene (X is any integer of 2 to 9) andbicyclo[4.3.0]-X-methyl-1,3-nonadiene (X is any integer of 2 to 9).Bicyclo[4.3.0]-2,9-nonadiene, bicyclo[4.3.0]-1,8-nonadiene,bicyclo[4.3.0]-3-methyl-2,9-nonadiene andbicyclo[4.3.0]-3-methyl-1,3-nonadiene are preferred; andbicyclo[4.3.0]-2,9-nonadiene is more preferred. These compounds can beused singly or in combination of two or more kinds. Incidentally,bicyclo[4.3.0]-2,9-nonadiene can easily be obtained by isomerization ofbicyclo[4.3.0]-3,7-nonadiene (which is being mass-produced industrially)using a dichlorotitanocene/lithium aluminum hydride catalyst(Tetrahedron Letters 1980, Vol. 21, pp. 637-640). Similarly,bicyclo[4.3.0]-1,8-nonadiene is obtained by isomerization ofbicyclo[4.3.0]-3,7-nonadiene; and bicyclo[4.3.0]-X-methyl-2,9-nonadieneand bicyclo[4.3.0]-X-methyl-1,3-nonadiene are obtained by isomerizationof bicyclo[4.3.0]-X-methyl-3,7-nonadiene (X is any integer of 2 to 9)and/or bicyclo[4.3.0]-X-methyl-3,8-nonadiene (X is any integer of 2 to9). The isomerization products of bicyclo[4.3.0]-3,7-nonadiene comprisebicyclo [4.3.0]-2,9-nonadiene, bicyclo[4.3.0]-1,8-nonadiene, etc.; and apart or the whole (one or a plurality of compounds) of the isomerizationproducts can be used as the monomer in the present invention. Further,the isomerization products of bicyclo[4.3.0]-3-methyl-3,7-nonadieneand/or bicyclo[4.3.0]-3-methyl-3,8-nonadiene comprise bicyclo[4.3.0]-3-methyl-2,9-nonadiene, bicyclo [4.3.0]-3-methyl-1,3-nonadiene,etc.; and a part or the whole (one or a plurality of compounds) of theisomerization products can be used as the monomer in the presentinvention.

With respect to the production process of the bicyclic conjugated dienepolymer of the present invention, there is no particular restriction.The polymer can be produced by cationic polymerization, anionicpolymerization, radical polymerization, coordination polymerization,etc., as in polymerization of a chain conjugated diene monomer such asbutadiene or the like. The catalyst or reaction initiator used in thesepolymerizations can be the same as used in polymerization of a chainconjugated diene monomer such as butadiene or the like.

The above polymerization may be conducted in water in an emulsifiedstate using a surfactant such as potassium or sodium salt ofdisproportionated rosin acid, formaldehyde condensate ofnaphthalenesulfonic acid or its potassium or sodium salt, sodiumformaldehyde sulfoxylate, or the like.

With respect to the catalyst used in cationic polymerization, there isno particular restriction. There can be used, for example, Lewis acidssuch as aluminum chloride, iron chloride, tin chloride, zinc chloride,strontium chloride, scandium chloride, titanium tetrachloride,trifluoroborate, trifluoroborate ether complex, trifluoroborate methanolcomplex, trifluoroborate phenol complex, trispentafluoroborate and thelike; protonic acids such as sulfuric acid, p-toluenesulfonic acid,hydrochloric acid, nitric acid and the like; alkyl aluminum chloride;and activated clay.

With respect to the catalyst used in anionic polymerization, there is noparticular restriction. There can be used, for example, alkyl lithiumssuch as n-butyl lithium, sec-butyl lithium, tert-butyl lithium and thelike; alkyl lithium/tetramethylethylenediamine mixtures; alkyl sodiumssuch as sodium methoxide and the like; alkyl potassiums such as cumylpotassium and the like; sodium naphthalene; distyryl dianion; metallicpotassium; metallic sodium; and metallic lithium.

With respect to the initiator used in radical polymerization, there isno particular restriction. There can be used, for example, dialkylperoxides such as ditertiary butyl peroxide and the like; diacylperoxides such as benzoyl peroxide and the like; azo compounds such asazobisisobutyronitrile and the like; disulfide compounds such astetra-alkyl thiuram disulfide and the like; and redox initiators such ashydrogen peroxide/iron salt type, benzoyl peroxide/dimethylaniline type,tetra-valent cerium salt/alcohol type and the like. By using such aradical initiator and, as necessary, by applying a heat or a light, aradical is generated.

With respect to the catalyst used in coordination polymerization, thereis no particular restriction. There can be used, for example,tetrachlorotitanium/triisobutyl aluminum, tetrachlorotitanium/triethylaluminum, dichlorocobalt/diethyl aluminum chloride,trichlorovanadium/triethyl aluminum, tetrachlorovanadium/triethylaluminum, and trisacetylacetonate vanadium/triethyl aluminum.

With respect to the solvents used in these polymerizations, there is noparticular restriction, and an ordinary solvent can be used. There canbe mentioned, for example, halogenated hydrocarbon type solvents such aschloromethane, dichloromethane, trichloromethane, tetrachloromethane,dichloroethane, trichloroethane, tetrachloroethane, tetrachloroethyleneand the like; aromatic hydrocarbons type solvents such as toluene,benzene, xylene, ethylbenzene and the like; aliphatic hydrocarbon typesolvents such as cyclohexane, mehtylcyclohexane, pentane, hexane,heptane and the like; and polar solvents such as acetone,dimethylformamide, tetrahydrofuran, methyl ethyl ketone, ethyl acetate,acetonitrile, diethyl ether, N-methylpyrrolidone and the like. Thesesolvents can be used singly or in combination of two or more kinds.Polymerization may be conducted without using any solvent.

The polymerization is conducted desirably between −150° C. and 150° C.,preferably between −100° C. and 100° C., more preferably −60° C. and 60°C. The polymerization temperature differs depending upon the type ofpolymerization. There is no particular restriction as to thepolymerization time, but it is preferred to conduct polymerizationwithin 24 hours.

The reaction mixture containing the thus-obtained polymer(s) can besubjected to a purification treatment by an ordinary method. When, forexample, reprecipitation is conducted, the reaction mixture is dissolvedin an appropriate good solvent (e.g. toluene or tetrahydrofuran) and theresulting solution is poured into an appropriate poor solvent (e.g.methanol, isopropyl alcohol, acetone or water), whereby the polymer(s)can be precipitated. The resulting precipitate is filtered to separateit from the solvent and then dried by heating under reduced pressure,whereby a polymer(s) can be obtained.

It is possible to subject the double bonds remaining in the polymer(s),to a chemical conversion such as hydrogenation, epoxidization,arylation, vulcanization or the like to obtain a modified bicyclicconjugated diene polymer(s).

Next, detailed explanation is made on the bicyclic conjugated dienecopolymer according to the second aspect of the present invention. Thebicyclic conjugated diene copolymer according to the second aspect ofthe present invention has, as the structural units, the above-mentionedbicyclic conjugated diene monomer of the general formula (I) and otherunsaturated compound.

There is no particular restriction as to the unsaturated compound usedin the present invention. As the compound, there can be selected atleast one compound preferably from olefins and diolefins of 2 to 10carbon atoms. As such olefins and diolefins, there can be mentioned, forexample, straight chain or branched chain olefins such as ethylene,propylene, butene, isobutene, pentene, hexene and the like; cyclicolefins such as cyclobutene, cyclopentene, cyclohexene,vinylcyclohexane, tetracyclododecene, norbornene or its derivatives, andthe like; aromatic olefins such as styrene, vinyltoluene, indene,divinylbenzene and the like; alicyclic diolefins such asdicyclopentadiene, tetrahydroindene, methyltetrahydroindene,vinylcyclohexene, vinylnorbornene, ethylidenenorbornene, cyclooctadiene,limonene and the like; conjugated dienes such as butadiene, isoprene,piperylene, chloroprene, cyclopentadiene, 1,3-cyclohexadiene and thelike; acrylonitrile; acrylic acid and its esters; methacrylic acid andits esters; and heteroolefins such as maleic anhydride, acrylamide,vinyl alcohol, vinyl acetate and the like. It is particularly preferablyto select from butadiene, isoprene, pierylene, chloroprene,acrylonitrile, propylene, isobutene and styrene.

With respect to the bicyclic conjugated diene copolymer according to thesecond aspect of the present invention, the polymerization process, thecatalyst used in cationic polymerization, the catalyst used in anionicpolymerization, the initiator used in radical polymerization, thecatalyst used in coordination polymerization, the solvent used in suchpolymerization, the temperature of polymerization, the time ofpolymerization, the treatment for purification, etc. are the same asthose employed in production of the bicyclic conjugated diene polymeraccording to the first aspect of the present invention.

As in the case of the bicyclic conjugated diene polymer according to thefirst aspect of the present invention, it is possible to subject thedouble bonds remaining in the obtained polymer(s), to a chemicalconversion such as hydrogenation, epoxidization, arylation,vulcanization or the like to obtain a modified bicyclic conjugated dienecopolymer.

There is no particular restriction as to the structure of the bicyclicconjugated diene copolymer according to the second aspect of the presentinvention. The bicyclic conjugated diene copolymer according to thesecond aspect of the present invention may have either of a straightchain structure, a branched chain structure and a cyclic structure. Thepolymerization type may be any of block polymerization, randompolymerization and alternating copolymerization, and they may be mixed.

The bonding form in the bicyclic conjugated diene monomer of the generalformula (I) in the second aspect of the present invention may be thesame bonding form as seen in polymerization of butadiene, that is,either or both of 1,4-bond and 1,2-bond. When the bonding form is thesame as 1,4-bond, a trans structure or a cis structure is formeddepending upon the structure of the bicyclic conjugated diene monomerused. Irrespective of the kind of the bonding form, the cyclic skeletonof bicyclic conjugated diene monomer after polymerization ischaracterized by having a 3-substituted unsaturated bond and possessinga planar structure (two-dimensional structure). Therefore,three-dimensional crosslinking is unlikely to take place, there hardlyoccurs entanglement between molecular chains of olefins in copolymer,and gelling is suppressed.

In the second aspect of the present invention, when the bicyclicconjugated diene monomers of the general formula (I) bond with eachother, there may take place bonding between (n+4)-membered ring and(m+4)-membered ring, bonding between (m+4)-membered ring and(m+4)-membered ring, and bonding between (n+4)-membered ring and(n+4)-membered ring.

EXAMPLES

The present invention is described specifically below by ProductionExamples and Examples. However, the present invention is not restrictedto these Examples. The following measuring apparatuses were used in theProduction Examples and the Examples. Number-average molecular weight(Mn) and weight-average molecular weight (Mw) of polymer were measuredusing GPC (Gel Permeation Chromatography) produced by ShimadzuCorporation. As the column, there were used TSK Guard Column HXL-L, TSKGel G 5000 HXL, TSK Gel G 4000 HXL, TSK Gel G 3000 HXL and TSK Gel G2000 HXL, all produced by Tosoh Corporation. The eluting solvent wastetrahydrofuran; the temperature was 40° C.; and the flow rate was 1.0ml/min. ¹HNMR (400 MHz) and ¹³CNMR (100 MHz) were measured using Lambda400 produced by Japan Electron Optical laboratory. Purity of organiccompound was measured using GC-17 A (gas chromatography) produced byShimadzu Corporation. As the column, TC-1 produced by ShimadzuCorporation was used; and the measuring conditions were 60° C. to 90° C.and 1° C./min (temperature elevation rate). Glass transition temperature(Tg) of polymer was measured using DCS 220 C produced by Seiko DenshiKogyo K.K. The measuring conditions were 70° C. to 250° C. and 20°C./min (temperature elevation rate). The ratio ofbicyclo[4.3.0]-2,9-nonadiene and bicyclo[4.3.0]-1,8-nonadiene wasmeasured using HP 6850 A (gas chromatography) produced byHewlett-Packard Co. As the column, HP-INNOWax produced byHewlett-Packard Co. was used. With respect to the measuring conditions,a sample was kept at 35° C. for 5 minutes; then, temperature elevationwas made to 135° C. at a rate of 5° C./min and further to 250° C. at arate of 10° C./min.

Monomer Production Example 1

Bicyclo[4.3.0]-2,9-nonadiene and bicyclo[4.3.0]-1,8-nonadiene (eachbeing a bicyclic conjugated diene monomer) were synthesized as followswith reference to Tetrahedron Letters 1980, Vol. 21, 63, 7–640. Into aflask purged with nitrogen were fed 97.4 g (0.81 mol) ofbicyclo[4.3.0]-3,7-nonadiene, 825 mg (3.3 mmol) of dichlorotitanoceneand 500 mg (13.2 mmol) of lithium aluminum hydride. Gradual temperatureelevation was made with stirring until the flask-inside temperaturereached 160° C. After the flask contents became a purple suspension,further 200 ml [177.1 g (1.47 mol)] of bicyclo[4.3.0]-3,7-nonadiene wasadded dropwise and stirring was made for 6 hours with the flask-insidetemperature being kept at 160° C. The same procedure was repeated threetimes to obtain 850 ml of a reaction mixture. To the reaction mixturewas added 200 ml of SAS 296 (a diarylalkane) produced by NipponPetrochemicals Co., Ltd. Then, flash distillation was conducted at 665Pa (5 mmHg) at 42 to 47° C. (top) to obtain 700 ml of a light yellowtransparent liquid. To the liquid was added 400 ml of SAS 296, afterwhich precision fractional distillation was conducted (length of column:70 cm, column packing: Helipack No. 3 (430 ml), pressure: 532 Pa (4mmHg), oil bath temperature: 75 to 80° C., reflux ratio=20/1) to obtain300 g of a colorless transparent liquid. The liquid had a purity of 99%or more when measured by gas chromatography and was found by ¹HNMR to bea 87/13 mixture of bicyclo[4.3.0]-2,9-nonadiene andbicyclo[4.3.0]-1,8-nonadiene (this mixture is hereinafter referred to asconjugated tetrahydroindene). The ¹HNMR chart and ¹³CNMR chart of theconjugated tetrahydroindene are shown in FIG. 1 and FIG. 2,respectively.

Monomer Production Example 2

Bicyclo[4.3.0]-3-methyl-2,9-nonadiene andbicyclo[4.3.0]-3-methyl-1,3-nonadiene (each being a bicyclic conjugateddiene monomer) were synthesized as follows. Into a flask purged withnitrogen were fed 28.7 g (0.21 mol) of a mixture (about 90/10) ofbicyclo[4.3.0]-3-methyl-3,7-nonadiene andbicyclo[4.3.0]-3-methyl-3,8-nonadiene and 200 mg (0.8 mmol) ofdichlorotitanocene. Gradual temperature elevation was made with stirringuntil the flask-inside temperature reached 130° C. Then, 12 ml (12 mmol)of a 1.0 M lithium aluminum hydride tetrahydrofuran solution was addedin small portions using a dropping funnel, in order to prevent theexcessive increase of flask-inside temperature. After the flask contentsbecame a purple suspension, stirring was made for 12 hours with theflask-inside temperature being kept at 130° C. After the temperature wasdecreased to room temperature, 1 ml of methanol was added, and thereaction mixture was filtered through a filter paper. The filtrate wassubjected to distillation under reduced pressure to remove the solvent,whereby a light yellow transparent liquid was obtained. The liquid wasanalyzed by gas chromatography and was found to be a mixture of 41% ofbicyclo[4.3.0]-3-methyl-2,9-nonadiene and 33% ofbicyclo[4.3.0]-3-methyl-1,3-nonadiene (this mixture is hereinafterreferred to as conjugated methyltetrahydroindene). The ¹HNMR chart and¹³CNMR chart of the conjugated methyltetrahydroindene are shown in FIG.3 and FIG. 4, respectively.

The following Examples 1 to 5 are each a synthesis example of bicyclicconjugated diene polymer by cationic polymerization.

Example 1

Into a flask purged with nitrogen were fed 25 ml of methylene chlorideand 5 ml of the conjugated tetrahydroindene obtained in the aboveProduction Example 1. Stirring was made with the flask-insidetemperature being kept at 0° C. Into the system was dropwise added 0.25ml of a solution of 0.1 ml of BF₃-ether complex (BF₃ content: 47%)dissolved in 10 ml of methylene chloride, followed by stirring for 20minutes. 50 ml of toluene was added to make a uniform solution. Thesolution was poured into 350 ml of methanol. The resulting white solidwas recovered by filtration under reduced pressure and vacuum-dried at130° C. to obtain 3.5 g of a white solid. The solid had good solubilityin toluene and, when measured for molecular weight by GPC, gave aweight-average molecular weight (Mw) of 16,700 and a number-averagemolecular weight (Mn) of 5,400. Also, the solid showed a Tg of 155° C.

Example 2

Into a flask purged with nitrogen were fed 25 ml of methylene chlorideand 5 ml of the conjugated tetrahydroindene obtained in the aboveProduction Example 1. Stirring was made with the flask-insidetemperature being kept at −40° C. Into the system was dropwise added0.25 ml of a solution of 0.1 ml of BF₃-ether complex (BF₃ content: 47%)dissolved in 10 ml of methylene chloride, followed by stirring for 60minutes. 50 ml of toluene was added to make a uniform solution. Thesolution was poured into 350 ml of methanol. The resulting white solidwas recovered by filtration under reduced pressure and vacuum-dried at130° C. to obtain 1.5 g of a white solid. The solid had good solubilityin toluene and, when measured for molecular weight by GPC, gave an Mw of31,800 and an Mn of 12,100. Also, the solid showed a Tg of 169° C. The¹HNMR and ¹³CNMR of the polymer obtained are shown in FIG. 5 and FIG. 6,respectively.

Example 3

Into a flask purged with nitrogen were fed 25 ml of methylene chlorideand 5 ml of the conjugated tetrahydroindene obtained in the aboveProduction Example 1. Stirring was made with the flask-insidetemperature being kept at 0° C. Into the system was dropwise added asolution of 106 mg of tris(pentafluorophenyl)borane dissolved in 0.5 mlof methylene chloride, followed by stirring for 3 minutes. 50 ml oftoluene was added to make a uniform solution. The solution was pouredinto 350 ml of methanol. The resulting white solid was recovered byfiltration under reduced pressure and vacuum-dried at 130° C. to obtain4.1 g of a white solid. The solid had good solubility in toluene and,when measured for molecular weight by GPC, gave an Mw of 39,600 and anMn of 11,400. Also, the solid showed a Tg of 166° C.

Example 4

Into a flask purged with nitrogen were fed 25 ml of methylene chlorideand 5 ml of the conjugated tetrahydroindene obtained in the aboveProduction Example 1. Stirring was made with the flask-insidetemperature being kept at −60° C. Into the system was dropwise added asolution of 109 mg of tris(pentafluorophenyl)borane dissolved in 0.5 mlof methylene chloride, followed by stirring for 6 minutes. 120 ml oftoluene was added to make a uniform solution. The solution was pouredinto 500 ml of methanol. The resulting white solid was recovered byfiltration under reduced pressure and vacuum-dried at 130° C. to obtain3.2 g of a white solid. The solid had good solubility in toluene and,when measured for molecular weight by GPC, gave an Mw of 78,800 and anMn of 36,000. Also, the solid showed a Tg of 167° C.

Example 5

Into a flask purged with nitrogen were fed 10 ml of methylene chlorideand 2.35 g of the conjugated methyltetrahydroindene obtained in theabove Production Example 2. Stirring was made with the flask-insidetemperature being kept at 0° C. Into the system was dropwise added asolution of 130 mg of tris(pentafluorophenyl)borane dissolved in 2 ml ofmethylene chloride, followed by stirring for 20 minutes. 1 ml ofmethanol was added. The reaction mixture was filtrated under reducedpressure using a filter paper and the filtrate was washed with toluene.The filtrate was then subjected to distillation under reduced pressureto remove the solvent, and the residue was vacuum dried at 30° C. toobtain a yellow, transparent, viscous liquid. The liquid had goodsolubility in toluene and, when measured for molecular weight by GPC,gave an Mw of 571 and an Mn of 318. The ¹HNMR and ¹³CNMR of the liquidare shown in FIG. 7 and FIG. 8, respectively.

Example 6

The following Example 6 is a synthesis example of bicyclic conjugateddiene polymer by anionic polymerization.

Into a flask purged with nitrogen were fed 20 ml of tetrahydrofuran, 2.3ml of n-butyl lithium (a 1.6 M hexane solution) and 0.7 ml oftetramethylethylenediamine. The mixture was stirred for 5 minutes. Tothe mixture was dropwise added 5 ml of the conjugated tetrahydroindeneobtained in the above Production Example 1, followed by stirring at roomtemperature for 3 hours. The resulting solution was poured into 500 mlof methanol. The resulting white solid was recovered by filtration underreduced pressure and vacuum-dried at 100° C. to obtain 1.8 g of a whitesolid. The solid had good solubility in toluene and, when measured formolecular weight by GPC, gave an Mw of 1,300 and an Mn of 1,000. Also,the solid showed a Tg of 98° C.

Example 7

The following Example 7 is a synthesis example of bicyclic conjugateddiene polymer by radical polymerization.

In a three-necked eggplant-shaped flask with a Dimroth condenser wereplaced 4.12 g of the conjugated tetrahydroindene obtained in the aboveProduction Example 1, 0.18 g of 2,2′-azobisisobutyronitrle and 30 ml oftoluene. Bubbling with argon was conducted for 1 hour. Then, the flaskinside was heated to 90° C. in an argon current, using an oil bath, togive rise to a reaction. The reaction was completed in 3 hours. Thereaction mixture was subjected to distillation under reduced pressure todistil off the light fractions. The residue was vacuum-dried at 30° C.to obtain a yellow, transparent, viscous liquid. The liquid was measuredby NMR. The ¹HNMR chart and ¹³CNMR chart of the liquid are shown in FIG.9 and FIG. 10, respectively. The liquid was also measured for molecularweight by GPC, which indicated a Mw of 569 and an Mn of 523.

Example 8

The following Example 8 is a synthesis example of bicyclic conjugateddiene polymer by coordination polymerization.

In a two-necked eggplant-shaped flask dried with N₂ was placed, in an N₂atmosphere, an ethylenebis(indenyl) zirconium (IV) dichloride/toluenesolution (2.4 mg/20 ml). Then, 2.0 ml of a toluene solution of 10% ofmethylaluminoxane was placed (the color of solution changed from yellowto orange). Thereafter, 9 ml of the conjugated tetrahydroindene obtainedin the above Production Example 1 was added. Stirring was made for 4hours and ethanol was added for quenching. Ethanol was further added anda white precipitate appeared. The precipitate was collected byfiltration under reduced pressure, washed with ethanol, and vacuum-driedat 40° C. to obtain 1.5 g of a solid. The solid showed a Tg of 141° C.

The polymers obtained in the above Examples 1 to 8 are each a bicyclicconjugated diene polymer having a structure not reported heretofore andcan be used in wide applications such as optical material, electronicmaterial, medical instrument, adhesive, lubricant and the like. Having abicyclic structure, they are expected to show high mechanical strengths.In particular, the polymers obtained in Examples 2 to 4 show a high Tgand have high heat resistance.

The following Examples 9 and 10 are each a synthesis example of abicyclic conjugated diene copolymer according to the second aspect ofthe present invention.

In addition to the measuring apparatuses used in the above Examples 1 to8, FT-730 produced by HORIBA, Ltd. was used for measurement of infraredabsorption spectrum (IR).

Example 9

Into a 200-ml autoclave were fed 95 ml of water, 0.016 g of tetrasodiumethylenediaminetetraacetic acetate hydrate, 0.05 g of sodium carbonate,0.2 g of tert-dodecylmercaptan, 0.0025 g of ferrous sulfateheptahydrate, 0.025 g of Rongalit, 0.25 g of Demol N (produced by KaoCorporation), 1.0 g of sodium 1-octanesulfonate, 5.0 g of the conjugatedtetrahydroindene obtained in the above Production Example 1 and 19 ml ofacrylonitrile. The inside of the autoclave was purged with N₂sufficiently. Subsequently, 45 ml of 1,3-butadiene was introduced. Afterthe mixture was cooled to 5° C., a solution of p-methane hydroperoxide(0.06 g)/acrylonitrile (1 ml) was introduced, and further 1 ml ofacrylonitrile for cleaning was introduced. After the reaction wasallowed to take place for 7 hours, then, 1.7 g of an aqueous solutioncontaining 10% of sodium dimethyldithiocarbamate was added. To thereaction mixture was added a 25% aqueous sodium chloride solution togive rise to salting-out. The resulting precipitate was collected byfiltration and vacuum-dried with heating, to obtain a slightly yellowrubbery substance. The ¹HNMR chart and IR chart of the rubbery substancewere shown in FIG. 13 and FIG. 14, respectively. Broad peaks derivedfrom the conjugated tetrahydroindene were confirmed at 1.2 ppm and 1.8ppm of ¹HNMR. A peak derived from the conjugated tetrahydroindene wasconfirmed in the vicinity of 1,700 cm⁻¹ of IR.

Example 10

Into a dried three-necked eggplant-shaped flask with a reflux condenserwere fed, using a syringe in an N₂ atmosphere, 10 ml of heptane, ahexane solution containing about 15% (0.0025 mol) of triisobutylaluminum, and a toluene solution containing 1.0 M titanium (IV) chloride(0.025 mol) in this order (the resulting mixture became a blacksuspension). Then, there was added a conjugated tetrahydroindene (2.6ml) (obtained in the above Production Example 1)/isoprene (8 ml)/hexane(40 ml) solution. The mixture was stirred for 5 hours in an oil bath of35° C. to give rise to a reaction. After the completion of the reaction,toluene was added to dissolve the precipitate formed in the reaction. Anaqueous hydrochloric acid solution was added for layer separation.Methanol was added to the organic layer for reprecipitation. Theresulting precipitate was vacuum-dried to obtain a light yellow, viscoussolid. The IR char of the solid is shown in FIG. 15. Peaks derived fromisoprene were confirmed at 1,400 cm⁻¹ and 1,660 cm⁻¹ and peaks derivedfrom the conjugated tetrahydroindene were confirmed at 1,700 cm⁻¹ and3,400 cm⁻¹.

INDUSTRIAL APPLICABILITY

As described above, the cyclic diene polymer according to the firstaspect of the present invention is produced from a cyclic diene monomereasy to produce and having a high polymerization activity, additionallyhas good solubility in solvents, and shows high heat resistance and highmechanical strengths.

The cyclic diene copolymer according to the second aspect of the presentinvention is produced from a bicyclic conjugated diene monomer easy toproduce and having a high polymerization activity, hardly gives rise togelling, is uniform and has good solubility, and can be allowed to havevarious functions.

1. A bicyclic conjugated diene polymer obtained by polymerizing amonomer comprising at least one kind of bicyclic conjugated dienemonomer represented by the following general formula (I):

wherein in the above general formula (I), R₁, R₂, R₃, R₄, R₅ and R₆ maybe the same or different from each other and are each a hydrogen atom, ahalogen atom, or an alkyl or halogenated alkyl group of 1 to 20 carbonatoms; n and m are each an integer of from 0 to 10; X₁, X₂, Y₁ and Y₂may be the same or different from each other and are each a hydrogenatom, a halogen atom, or an alkyl or halogenated alkyl group of 1 to 20carbon atoms; and, when m or n is 2 or more, each of mX₁'s, mX₂'s, nY₁'sand nY₂'s may be the same or different from each other.
 2. A bicyclicconjugated diene polymer according to claim 1, wherein the bicyclicconjugated diene monomer comprises bicyclo[4.3.0]-2,9-nonadienerepresented by R₁=R₂=R₃=R₄=R₅=R₆=H, n=2, m=1, and X₁=X₂=Y₁=Y₂=H in thegeneral formula (I).
 3. A bicyclic conjugated diene polymer according toclaim 1, wherein the bicyclic conjugated diene monomer comprisesbicyclo[4.3.0]-2,9-nonadiene represented by R₁=R₂=R₃=R₄=R₅=R₆=H, n=2,m=1, and X₁=X₂=Y₁=Y₂=H in the general formula (I) andbicyclo[4.3.0]-1,8-nonadiene represented by R₁=R₂=R₃=R₄=R₅=R₆=H, n=1,m=2, and X₁=X₂=Y₁=Y₂=H in the general formula (I).
 4. A bicyclicconjugated diene polymer according to claim 2, wherein the bicyclicconjugated diene monomer is a part or the whole of the isomerizationproducts of bicyclo-[4.3.0]-3,7-nonadiene.
 5. A bicyclic conjugateddiene polymer according to claim 1, wherein the bicyclic conjugateddiene monomer comprises bicyclo[4.3.0]-3-methyl-2,9-nonadienerepresented by R₁=R₂=R₃=R₄=R₆=H, R₅=CH₃, n=1, m=2, and X₁=X₂=Y₁=Y₂=H inthe general formula (I).
 6. A bicyclic conjugated diene polymeraccording to claim 1, wherein the bicyclic conjugated diene monomercomprises bicyclo[4.3.0]-3-methyl-2,9-nonadiene andbicyclo[4.3.0]-3-methyl-1,3-nonadiene represented by R₁=R₂=R₃=R₄=R₆=H,R₅=CH₃, n=1, m=2, and X₁=X₂=Y₁=Y₂=H in the general formula (I).
 7. Abicyclic conjugated diene polymer according to claim 5, wherein thebicyclic conjugated diene monomer is a part or the whole of theisomerization products of bicyclo-[4.3.0]-3-methyl-3,7-nonadiene.
 8. Amodified bicyclic conjugated diene polymer obtained by chemicalconversion of the bicyclic conjugated diene polymer set forth inclaim
 1. 9. A bicyclic conjugated diene copolymer obtained bycopolymerizing a monomer comprising at least one kind of bicyclicconjugated diene monomer represented by the following general formula(I), with at least one kind of unsaturated compound other than saidmonomer:

wherein in the above general formula (I), R₁, R₂, R₃, R₄, R₅ and R₆ maybe the same or different from each other and are each a hydrogen atom, ahalogen atom, or an alkyl or halogenated alkyl group of 1 to 20 carbonatoms; n and m are each an integer of from 0 to 10; X₁, X₂, Y₁ and Y₂may be the same or different from each other and are each a hydrogenatom, a halogen atom, or an alkyl or halogenated alkyl group of 1 to 20carbon atoms; and, when m or n is 2 or more, each of mX₁'s, mX₂'s, nY₁'sand nY₂'s may be the same or different from each other.
 10. A bicyclicconjugated diene copolymer according to claim 9, wherein the bicyclicconjugated diene monomer comprises bicyclo[4.3.0]-2,9-nonadienerepresented by R₁=R₂=R₃=R₄=R₅=R₆=H, n=2, m=1, and X₁=X₂=Y₁=Y₂=H in thegeneral formula (I).
 11. A bicyclic conjugated diene copolymer accordingto claim 9, wherein the bicyclic conjugated diene monomer comprisesbicyclo[4.3.0]-2,9-nonadiene represented by R₁=R₂=R₃=R₄=R₅=R₆=H, n=2,m=1, and X₁=X₂=Y₁=Y₂=H in the general formula (I) andbicyclo[4.3.0]-1,8-nonadiene represented by R₁=R₂=R₃=R₄=R₅=μR₆=H, n=1,m=2, and X₁=X₂=Y₁=Y₂=H in the general formula (I).
 12. A bicyclicconjugated diene copolymer according to claim 10, wherein the bicyclicconjugated diene monomer is a part or the whole of the isomerizationproducts of bicyclo-[4.3.0]-3,7-nonadiene.
 13. A bicyclic conjugateddiene copolymer according to claim 9, wherein the unsaturated compoundis at least one kind selected from olefins and diolefins all of 2 to 10carbon atoms.
 14. A bicyclic conjugated diene copolymer according toclaim 13, wherein the unsaturated compound is at least one kind selectedfrom butadiene, isoprene, piperylene, chloroprene, acrylonitrile,ethylene, propylene, isobutene and styrene.
 15. A modified bicyclicconjugated diene copolymer obtained by chemical conversion of a bicyclicconjugated diene copolymer set forth in claim 9.